Hydrocarbon conversion process

ABSTRACT

A process wherein a hydrocarbon feedstream comprising heavy hydrocarbons is simultaneously coked, partially desulfurized, hydrogenated, cracked and partially converted to a hydrogencontaining gas in the presence of an alkali metal containing catalyst.

United States Patent Aldridge June 11, 1974 HYDROCARBON CONVERSION PROCESS [75] Inventor: Clyde L. Aldridge, Baton Rouge. References Cited UNITED STATES PATENTS [73] Assignee: Esso Research and Engineering 3,179,584 4/1965 Hamner et al. 208/106 Company, Linden, N 3,726,791 4/l973 Kimberlin et al. 208/127 3,740,193 6/1973 Aldridge et al. .4 48/202 [22] Filed: Dec. 20, 1972 [21 1 App]. No.: 316,836 Primary Examiner-Delbert E. (iantz Related us. Application Data Assistant ExammerG. E. Schm1tkons [63] Continuation-impart of Ser. No. l25.58l, March 18,

1971, abandoned. ABSTRACT v A process wherein a hydrocarbon feedstream compris- U-S. R, heavy hydrocarbons is imultaneously coked par- 455/215, 208/53, 208/57, 208/53, tially desulfurized, hydrogenated, cracked and par- 208/264, 252/425, 252/444 tially converted to a hydrogen-containing gas in the [51 ll]!- presence of an metal containing catalyst. [58] Field of Search 208/112; 48/197 R, 214,

19 Claims, 1 Drawing Figure PATENTEDJUNHIQM v 3.816298 I04 no I09 nos 1 HYDROCARBON CONVERSION PROCESS CROSS REFERENCE TO RELATED APPLICATIONS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a process for upgrading hydrocarbon feedstreams containing heavy hydrocarbons into liquid hydrocarbon products and a hydrogencontaining gas in the presence of a particulate alkali metal containing catalyst.

2. Description of the Prior Art The use of alkali metal compounds as catalysts in various hydrocarbon conversion processes is well known. It is known (see US. Pat. No. 3,112,257) that hydrocarbon oils can be desulfurized by contact with steam in the presence of a Group VI to Group VIII metalalkali metal catalyst at temperatures under 900F. Alkali metal compounds are also known to increase hydrogen production when steam gasifying solid carbonaceous materials (see US. Pat. No. 3,252,773) and when coking hydrocarbon oils at conventional fluid coking conditions (see US. Pat. No. 3,179,584). It is also known to use minor amounts of alkali metals to stabilize rhenium catalysts used in the production of hydrogen from normally gaseous or normally liquid light hydrocarbons (see U.S. Pat. Nos. 3,449,078 and 3,530,194). As disclosed in US. Pat. No. 3,252,774, it is further known that liquid hydrocarbons can be converted to a hydrogen rich gas stream by contact with steam and a large excess of a molten alkali metal catalyst system at low feed rates.

Furthermore, it is known to produce gasoline boiling range hydrocarbons together with a fuel gas from heavy liquid hydrocarbons in a two-zone process wherein a high temperature combustion zone is operated in conjunction with a hydrocracking zone containing inert particulate contact material (see US. Pat. No. 3,202,603).

Conventional fluid coking processes produce liquid products which generally contain large amounts of sulfur compounds as well as unsaturated hydrocarbon products. It has now been found that a hydrocarbon feedstream comprising at least wt. hydrocarbons having a boiling point above 600F. can be converted into normally liquid hydrocarbon products which are partially desulfurized and hydrogenated, as well as a hydrogen-containing gaseous product by conducting the process under specified conditions and in the presence of a particulate alkali metal containing catalyst.

SUMMARY OF THE INVENTION In accordance with the invention, a hydrocarbon feed containing at least 10 weight percent hydrocarbons having a boiling point above 600F.,' at atmospheric pressure, is converted to a normally liquid hydrocarbon product and a hydrogen containing gas by contacting said hydrocarbon feed with a hydrogen and carbon oxide-containing gas in a first reaction zone containing a particulate catalyst bed comprising an alkali metal component, a solid particulate support and an in-situ formed carbonaceous deposit on said support, wherein said alkali metal component (calculated as the metal) comprises at least 1.0 weight percent of the total solids inventory of said bed, and said first reaction zone is maintained at a pressure above 150 psig and at an average temperature between about 700 and 1,100F. to produce a normally liquid, partially desulfurized hydrocarbon product, a hydrogen-containing gas and solid carbonaceous material, at least a portion of which deposits on said support during said contact ing. Thereafter, at least a portion of the particulate catalyst is forwarded to a second reaction zone maintained at a pressure above 150 psig and at an average temperature above 1,200F. and contacted with steam at a steam-to-hydrocarbon feed ratio of between 0.05 and 10 weight parts of steam to weight part of hydrocarbon feed of the first reaction zone, to produce a hydrogen and carbon oxide-containing gas. At least a portion of the hydrogen and carbon oxide-containing gas produced in the second reaction zone is passed to the first reaction zone. A vaporous product comprising partially desulfurized, normally liquid, hydrocarbon products and a hydrogen-containing gas is recovered from the first reaction zone.

The term normally liquid hydrocarbons as used herein is intended to include hydrocarbons whose atmospheric pressure boiling points are greater than F.

In one embodiment of the invention, the hydrocarbon products are separated into ligher and heavier fractions, and at least a portion of the heavier fraction is recycled to the first reaction zone.

In another embodiment of the invention, an oxygencontaining gas, such as air or oxygen, may also be introduced into the second reaction zone to promote the combustion of at least a portion of carbonaceous material and/or gaseous products contained therein to supply thereby at least a portion of the process heat requirements.

BRIEF DESCRIPTION OF THE DRAWING The figure shown in the accompanying drawing is a diagrammatic flow plan of a preferred embodiment of this invention.

PREFERRED EMBODIMENT OF THE INVENTION The preferred embodiment of the invention will be described with reference to the figure.

The process of this invention is suitable for the conversion of a great variety of hydrocarbon feedstreams containing heavy hydrocarbons and which may further contain contaminants such as sulfur compounds, metals and/0r nitrogen compounds. It is suited for the treatment of hydrocarbon feeds containing at least 10 weight percent hydrocarbons boiling above 600F. at atmospheric pressure and it is especially suited for hydrocarbon feeds containing at least 10 weight percent hydrocarbons having a boiling point greater than 900F. at atmospheric pressure. By way of example, suitable hydrocarbon feeds include whole petroleum crude; petroleum atmospheric residuum; petroleum vacuum residuum; heavy hydrocarbon oils and other heavy hydrocarbon residua; deasphalted residua; the asphaltene fraction from deasphalting operations; bottoms from catalytic cracking process fractionators; coker produced oils; cycle oils, such as catalytically cracked cycle oils; pitch, asphalt and bitumen from coal, tar sands or shale; naturally occurring tars, as well as, tars resulting from petroleum refining processes; shale oils; tar sand oils which may further contain sand; hydrocarbon feedstreams containing heavy or viscous materials including petroleum wax fractions, etc. Furthermore, to any of these suitable hydrocarbon feeds may be added a solid carbonaceous material such as coke or coal.

Referring to the figure, a hydrocarbon feedstream is introduced by line 101 into a first reaction zone 102 to contact a hydrogen and carbon oxide-containing gas in the presence of a particulate alkali metal containing catalyst maintained as a fluid bed 103. The hydrogen and carbon oxide-containing gas is produced in a second reaction zone to be described below. This gas will aid in keeping the catalyst bed in fluidized state. If desired, an additional fluidizing gas may also be introduced into the first reaction zone.

The catalyst may be maintained in the first reaction zone as a fixed, moving or fluid bed. Moving or fluid bed catalyst systems are preferred for conversion of feed materials containing the heaviest hydrocarbons. Because of theease of maintaining uniform temperature distribution and preventing the formation of coke agglomerates, a fluidized catalyst system is particularly preferred for the conversion of feedstocks containing large amounts of hydrocarbons having a 900F.+ boiling point at atmospheric pressure.

Catalyst bed 103 is a bed of particulate solids which contains the catalyst, coke by-product and ash constituents including metal contaminants of the hydrocarbon feed. The catalyst comprises an alkali metal component, a solid particulate material as carrier or support and a solid carbonaceous coating or deposit which is formed in-situ on the support when the process is in operation. The active catalytic component is believed to be the alkali metal. The alkali metal component is preferably provided in the catalyst system by either depositing or mixing initially an alkali metal compound with a suitable solid particulate support. This depositing or mixing can be performed within the reaction vessel or outside the reaction vessel with subsequent introduction of the composite into the reaction vessel. Under the process conditions, it is believed that the alkali metal compound is at least partially reduced to the free metallic state.

Suitable alkali metal catalyst components include the carbonates, acetates, formates, sulfides, hydrosulfides, sulfites, vanadates, oxides and hydroxides of sodium, lithium, cesium and potassium. In general, any alkali metal compound which is at least partially reducible to the free metallic state under process conditions may be used.

The solid particulate support may be chosen from a wide variety of solids. The support may be a gasifiable (at process conditions) solid or a substantially nongasifiable (at process conditions) solid. Although a gasifiable solid such as coke or activated carbon is suitable as support, a non-gasifiable solid support is preferred because changes of temperature or other process con ditions in the reaction zone could result in degradation of the gasifiable support, including partial or total loss of the support from the bed and the possible consequent entrainment of alkali metal containing fines out of the reaction zone. The preferred non-gasifiable particulate solid supports include zeolites, refractory inorganic oxides, such as, silica-alumina, zirconia, magnesia, calcium oxide, gamma alumina, crude or partially purified bauxite, alpha alumina, alundum, mullite, silica; synthetically prepared or naturally occurring materials such as pumice, clay, diatomaceous earth (kieselguhr); porcelain, glass or marble spheres or other inert spherical materials.

The carbonaceous deposit is formed when the process is in operation. Part of the feed is converted to a solid carbonaceous material, a portion of which deposits on the alkali metal containing support particles present in the first reaction zone. While applicant does not wish to be bound by theory, it is believed that at least a portion of the alkali metal migrates to the carbonaceous deposit on the support to form the desired catalyst system.

A preferred catalyst comprises K CO or Cs CO mixed with or deposited on a refractory inorganic oxide such as alumina, silica, silica-alumina, magnesia, crude or partially purified bauxite or mixtures thereof. A sufficient amount of the alkali metal compound is added to the catalyst bed to maintain at least 1.0 weight percent alkali metal (calculated as the metal) based on the total bed solids inventory (support plus alkali metal compound, solid carbonaceous products, ash, residual metals, etc.) present in the catalyst bed under processing conditions. Preferably, the weight of alkali metal in the bed will range broadly between 1.0 and 35 weight percent (calculated as the metal), more preferably between 3 and 30 weight percent and most preferably between 4 and 25 weight percent. An example of an equilibrium composition of the total solids inventory of the catalyst bed would be about 25 weight percent K CO (calculated as K CO 35 weight percent solid support, 20 weight percent coke, 20 weight percent ash derived from impurities of the feed. A portion of the catalyst bed solids may be withdrawn from the system periodically or continuously to prevent excessive accumulation of ash in the bed. Fresh or regenerated catalyst wouldthen be introduced intothe system to maintain the desired catalyst inventory. The catalyst system exhibits an unusually high cracking activity. To those catalysts may be added, if desired, components from Group V, VI, VII and Vlll of the Periodic Chart as well as the Lanthanides and Actinides. Especially beneficial are compounds of V, Cr, Fe, Co, Ni, Mo and W. Furthermore, it is believed that metal contaminants of the feed, such as vanadium and nickel, which deposit in the catalyst bed under operating conditions enhance the desired reactions.

The first reaction zone is maintained at a pressure above psig (pounds per square inch gauge), Preferably at a pressure between about 200 and 800 psig, more preferably at a pressure between about 300 and 500 psig and at a numerically integrated average temperature between about 700 and l,l0OF., preferably between about 900- and l,000F. By numerically inte grated average temperature is meant the procedure wherein a temperature-distance plot (curve) is averaged by taking the sum of n equally spaced ordinate values of temperature and dividing the sum by n.

The rate at which the hydrocarbon feedstream is fed into the first reaction zone will depend in part upon the operating conditions within that zone. Under the above given operating conditions, suitable feed rates would be, for'example, 0.1 to 1.5 weight part of feed per weight part of bed solids inventory per hour, preferably 0.2 to 0.6 weight part of feed per weight part of bed solids inventory per hour.

At least a portion of the heat required in the first reaction zone is supplied from the second reaction zone via circulation of hot solids as will be described more fully below.

It may be necessary to provide additional heat into the first reaction zone. This may be done in several ways. The hydrocarbon feedstream may be preheated to a temperature between 400 and 950F. before introduction into the first reaction zone. A further method would include electrical heating of the catalyst bed or other indirect methods of heating the bed. Furthermore, any combination of each of these methods could also be employed.

Treatment of the hydrocarbon feedstream in the first reaction zone produces a vaporous product and a solid carbonaceous material, a portion of which deposits on the particulate alkali metal containing support particles. The vaporous product comprises hydrocarbon products including normally liquid hydrocarbons and a hydrogen-containing gas.

A portion of the particulate catalyst including the solid carbonaceous deposition is passed via line 104 to a second reaction zone 105. The second reaction zone is maintained at a pressure above 150 psig, preferably at a pressure between 200 and 800 psig and more preferably at a pressure between 300 and 500 psig. The temperature in the second reaction zone is maintained to be at least a numerically integrated average of 1,200F., preferably at a numerically integrated average temperature varying between about 1,200 and In the second reaction zone, at the start of the process is maintained a bed 106 of the same catalyst as that initially employed in the first reaction zone. When the process is in operation, there is interchange of a portion of the catalyst particles between the first and second reaction zones via line 104 and the second and first reaction zones via line 110. The carbon content of the catalyst bed of the second reaction zone will be lower than that of the first reaction zone when the process is in operation.

Steam is introduced into the second reaction zone 105 via line 107 such that the steam-to-hydrocarbon feed of the first reaction zone is between about 0.05 and weight part of steam per weight part of hydrocarbon feed, preferably between 0.15 and 0.9 weight parts of steam per weight part of feed, more preferably between 0.3 and 0.75 weight part of steam per weight part of feed.

Because the reaction of steam with the carbonaceous material in the second reaction zone is an endothermic reaction, it may be necessary to add heat to that zone. A preferred method of providing at least a portion of the heat is by injecting small quantities of an oxygencontaining gas, such as air or oxygen, into the second reaction zone, for example, at the bottom of the second reaction zone via line 108 or the oxygen-containing gas may be injected with the steam via line 107. The oxygen-containing gas will then react with the carbon present in the second reaction zone to produce the following exothermic reaction:

When an oxygen-containing gas is introduced into the second reaction zone, the amount injected is that quantity required to maintain the desired temperature.

Other methods of providing at least a portion of the heat requirement of the second reaction zone include withdrawing a portion of the catalyst bed solids from the second reaction zone and circulating that portion to a separate heating zone such as, for example, an air burner, and recycling the resulting heated portion to the second reaction zone.

Heat may also be provided by other methods such as preheating the steam or electrical heating of the catalyst bed or other indirect heating methods. Furthermore, any combination of each of these methods could also be employed.

The catalyst may be maintained in the second reaction zone as a fixed, moving or fluid bed, the latter two being preferred.

At least a portion of the carbonaceous material deposition reacts with steam under the above-given conditions in the second reaction zone to produce a gaseous product comprising H CO and CO At least a portion of the gaseous product of the second reaction zone is passed to the first reaction zone via line 109 to provide the hydrogen and carbon oxide containing gas required in the first reaction zone for the desulfurization and hydrogenation reactions, as well as to aid in keeping the bed of the first reaction zone fluidized. Since this gaseous product may contain unreacted steam, if desired, the gaseous product of the second reaction zone may be treated (e.g., by condensation) to remove unreacted steam and, if desired, further treated, by conventional means, to remove any CO which may be present prior to passing at least a portion of the remaining gaseous product to the first reaction zone.

The vaporous product of the first reaction zone is then removed from the first reaction zone via line 111 to recover partially desulfurized hydrocarbon products and a hydrogen-containing gas. The hydrocarbon products may further be separated into ligher and heavier fractions. If desired, at least a portion of the heavier fractions may be recycled to the first reaction zone. If further desired, at least a portion of the hydrogencontaining gaseous product recovered from the first reaction zone may also be recycled to either reaction zone.

It is to be understood that the two-stage process of this invention may be carried out in a single vessel or in two separate vessels.

The following example is illustrative of various embodiments of the invention.

EXAMPLE Several runs were made in an isothermal coking unit containing a stirred fluid bed under conditions to simulate the first stage of two-stage process of this invention. The feed-stock used was a Safaniya vacuum residuum having an initial boiling point of l,00OF.+ at atmospheric pressure, an API gravity of 4.56, a Conradson carbon residue of 20.62 weight percent and a sulfur content of 5.1 weight percent. The coking unit consisted of a stirred reaction vessel ofO. 197 cubic foot capacity, a feed system and a product recovery system.

The reactor temperature was controlled by having the reactor immersed in a heated fluidized sandbath. A mixture of feed, steam and/or simulated gas product of the second stage (gasification) of the present invention entered the bottom of the reaction vessel. Reactor effluent passed through an outlet filter to retain entrained solids within the reaction zone. Steam was injected into the reactor overhead line to prevent coking. Two product accumulators in series, one hot (about 250 to 270F.) and the other cold (about 50F.) were utilized to prevent oil-in-water emulsions and attendant product recovery problems, and provide a split in the C -C5 boiling range. The product gas was metered and sam-v pled while the feed and product accumulators were weighed at the start and end of each run. Coke yield was obtained by weighing the solids at the start and at the end of the run. The total liquid product was decanted to remove water and charged to a stirred vacuum still to complete water separation and take overhead all the 1,015F minus material. The 1,015F. plus material constituted stirred vacuum still bottoms. Total stirred vacuum still overhead was fractionated in a /5 still to yield gasoline, heating oil and gas oil cuts. The gaseous products were analyzed by mass spectroscopic analysis. The liquid products were analyzed for sulfur content and unsaturation by conventional methods.

Run No. 1 was carried out at standard fluid coking 15 conditions 10 psig pressure) using mullite as the fluidized contact material and steam as the fluidizing gas. The use of mullite as contact material is known to give equivalent results in fluid coking runs as the use of fluid coke as contact material.

In run No. 2, the pressure was increased to 190 psig and a gas blend containing hydrogen was injected into the vessel. Run No. 2 also differed from run No. 11 in that no steam was added to the reaction zone. The contact material was again mullite.

Run 3 to 7 simulated the first stage of the two-stage process of the present invention.

Potassium carbonate was impregnated on various particulate solid supports by conventional impregnation methods and the alkali metal containing supports were then introduced into the reaction vessel or runs 3 to 7 as the fluidized solids. 1n run 7, the gamma alumina support was impregnated with cobalt and molybdenum components as well as potassium carbonate. 1n runs 3 to 7, a hydrogen and carbon oxide-containing gas blend such as would be obtained in the second stage (gasification stage) of the present invention was introduced into the reactor as well as steam.

As can be seen from Tables 1 and 11, runs 3 to 7 which were runs simulating the first stage of the process of the presend invention showed a greater degreeof unsaturation reduction and/or improved desulfurization of the C to 1015F. liquid products over the fluid coking runs. Increasing the pressure of standard fluid coking, including the addition of a hydrogen-containing gas (hydrogen partial pressure of 94.6 psig) as carried out in run No. 2 had no perceptible effect on liquid product desulfurization. Run 7 showed the greatest degree of desulfurization of the liquid products. Runs 3 to 7 also showed greater degree of unsaturation reduction and an increase in paraffin content of the liquid products than did run 1 or run 2. The product quality of the C5/430F. fraction obtained in runs 1 to 7 is tabulated in Table 11.

Since unsaturated compounds in the final fuel product are responsible for the resulting gumming when used in a combustion engine, it is highly desirable to decrease their percentage in the fuel. Since parafiins can be converted to aromatics easily in later processing steps and since aromatics raise the octane number, an increase in their concentration at this point of the refinery operation ,will result in more economically producing a fuel of the desired octane.

TABLE I PROCESS DATA AND YlE LDS Run No. 1 2 3 4 5 6 7 Minutes Fluidized Solids, Type Mullite Mullite Alpha A1 0 Porocel Gamma A1 0 Gamma-A1 0:

CO-MO Alkali metal None None 10 wt. K CO; cc. 24 gms. 4774 5286 3904 3228 2283 2478 2520 Reactor Pressure. psig 10 345 342 352 350 350 Temperature. F. 965 960 930 922 911 922 915 Hydrogen Partial Press. psig 0.2 94.6 92.5 100.2 108 119.6 71.7

Feed Rate, Wt. feed/WLbed solids/Hr. 0.24 0.20 0.3 0.31 0.52 0.52 0.55 Steam. Wt. 71 on Feed 12.9 0 58.1 64.1 51.8 47.2 42.9

Recycle Gas. Wt. 7r on Feed 1 0 5.39 3.83 4.19 4.04 2.5 2.49 CO 0 1.11 12.47 14.41 12.48 7.65 8.40 H S O 0 0.70 0.86 0 0.41 0.81 C0 0 0.28 56.68 64.33 56.45 34 42 35.28 CH 0 32.24 6.11 6.88 6.10 3 68 3.45 Vapor Holding Time. Total Sec.' 19.9 20.8 30.8 24.8 36.5 37.6 36.63

H O Conversion -0.05 0.08 7.79 15.06 1" 11 2 .75 1.26

Yields. Wt. r on Feed H, 0.05 0.42 0.48 1.03 0.71 1.60 0.2 CO 0.03 0.92 1.44 4.82 4.45 0.89 4.23 H 5 0.15 0.17 1.23 1.73 1.93 1.00 2.42 C0 0.04 0.25 10.66 22.19 18.36 32.18 1.77 C:,- 5.66 11.96 9.05 9.20 6.92 8.50 10.32 C 1.58 3.10 3.84 3.80 3.33 2.78 2.54 C /430F. 11.73 10.38 13.72 15.39 19.30 13.24 13.99 430/650F. 9.56 11.18 11.53 15.38 17.37 16.71 15.72 650/1015F. 28.23 26.97 26.12 22.18 23.69 26.18 19.15 1015F.+ 19.60 8.52 6.35 1.68 0.97 1.66 4.74 Coke. gross 23.71 28.07 30.94 31.78 27.64 31.96 33.46 net 23.71 28.07 26.90 27.26 24.39 23.19 33.56

TABLE I Continued PROCESS DATA AND YIELDS Run No. l 2 3 4 5 6 7 Sulfur. Wt. 7r

Cfl/430 F 0.83 0.85 0.85 0.61 0.75 0.78 0.44

Coke 9.31 9.47 6.78 6.54 6.80 7.74 4.41

Legend:

"' Dense phase plus disperse phase. Gross minus carbon in C CO Net Porocel is trademark name of Amipulgus (lay Co. for bauxite.

TABLE II PRODUCT QUALITY Run N0. 1 2 3 4 5 6 7 Aromatics 21.3 26.3 25.3 27.7 30.9 24.5 23.9

% Unsats. 56.7 49.3 34.7 37.9 32.6 36.9 34.7

% Paraffins 22 24.3 40.0 34.4 36.5 38.6 41.4

Bromine No. 104.2 81.6 57.9 71.6 58.9 65.6 67.9

gm./l00 gm. Aniline Point, 83 86.0 90.5 89 104.5 101 What is claimed is: 2. The process of claim 1, wherein the weight of said 1. A process for producing a partially desulfurized normally liquid hydrocarbon product and a hydrogencontaining gas from a hydrocarbon feed containing at least 10 weight percent hydrocarbons having a boiling point above 600F., at atmospheric pressure, which comprises:

a. contacting said hydrocarbon feed with a hydrogen and carbon oxide-containing gas in a first reaction zone containing a particulate catalyst bed comprising an alkali metal component, a solid particulate support, and an in-situ formed carbonaceous de posit on said support, wherein said alkali metal component (calculated as the metal) comprises at least 1.0 weight percent of the total solids inventory of said bed, said first reaction zone being maintained at a pressure above 150 psig and at an average temperature between about 700 and 1,100F. to produce a normally liquid partially desulfurized hydrocarbon product, a hydrogencontaining gas, and solid carbonaceous material, at least a portion of which deposits on said support during said contacting step;

b. passing at least a portion of said particulate catalyst into a second reaction zone maintained at a pressure above 150 psig and at an average temperature above 1,200F. and contacting the same with steam at a steam-to-hydrocarbon feed ratio of between 0.05 and 10 weight parts of steam to weight part of hydrocarbon feed of the first reaction zone, to produce a hydrogen and carbon oxidecontaining gas; I

c. passing at least a portion of said hydrogen and carbon oxide-containing gas to said first reaction zone, and

d. recovering partially desulfurized hydrocarbon products and a hydrogen-containing gas from the first reaction zone. I

alkali metal component (calculated as the metal) is between ].0 and 35 weight percent of the total solids inventory of said bed.

3. The process of claim 1, wherein the weight of said alkali metal component (calculated as the metal) is between 3 and 30 weight percent of the total solids inventory of said bed.

4. The process of claim 1, wherein said alkali metal component (calculated as the metal) is between 4 and 25 weight percent of the total solids inventory of said bed.

5. The process of claim 1, wherein said alkali metal component is an alkali metal compound which is at least partially reducible to the free metal.

6. The process of claim 1, wherein said solid support is a non-gasifiable material.

7. The process of claim 1, wherein said solid support is a refractory inorganic oxide.

8. The process of claim 1, wherein said solid support is an inorganic oxide selected from the group consisting of silica, alumina, silica-alumina, magnesia, crude or partially purified bauxite or mixtures thereof.

9. The process of claim 1, wherein said solid support is activated carbon.

10. The process of claim 1, wherein said solid support is petroleum coke.

11. The process of claim 1, wherein said catalyst comprises K CO or Cs CO deposited on or mixed with said support.

12. The process of claim 1, wherein said first and second reaction zones are each maintained at a pressure between 200 and 800 psig.

13. The process of claim 1, wherein said first reaction zone is maintained at an average temperature between 900 and 1,000F. and said second reaction zone is maintained at an average temperature between 1,200 and l,500F.

14. The process of claim 1, wherein an oxygencontaining gas is introduced into said second reaction zone.

15. The process of claim 1, wherein a portion of the catalyst bed solids of the second reaction zone is passed to a separate heating zone and wherein at least a portion of the thus heated solids is recycled to said second reaction zone to provide a portion of the heat needed in that zone.

16. The process of claim 1, wherein the hydrocarbon product is separated into lighter and heavier fractions and wherein at least a portion of the heavier fraction is recycled to said first reaction zone.

17. The process of claim 1, wherein said hydrocarbon feedstream comprises at least weight percent hydrocarbons having a boiling point above 900F.

18. A process for producing a partially desulfurized normally liquid hydrocarbon product and a hydrogencontaining gas from a hydrocarbon feed containing at least 10 weight percent hydrocarbons having a boiling point above 600F. at atmospheric pressure, which comprises:

a. contacting said hydrocarbon feed with a hydrogen and carbon oxide-containing gas in a first reaction zone containing a particulate catalyst bed comprising an alkali metal component, a non-gasifiable solid particulate support and an in-situ formed car- 12 bonaceous deposit on said support, wherein the alkali metal component (calculated as the metal) comprises at least 1.0 weight percent of the total solids inventory of said bed, said first reaction zone being maintained at a pressure above 150 psig and at an average temperature between about 700 and l,l0OF. to produce a normally liquid partially desulfurized hydrocarbon product, a hydrogencontaining gas and solid carbonaceous material, at least a portion of which deposits on said support during said contacting step;

b. passing at least a portion of said particulate catalyst into a second reaction zone maintained at a pressure above 150 psig and at an average temperature between about 1,200F. and 1,500F. and contacting the same with an oxygen-containing gas and with steam at a steam-to-hydrocarbon feed ratio of between 0.05 and 10 weight parts of steam to weight part of hydrocarbon feed of the first reaction zone to produce a hydrogen and carbon oxidecontaining gas, and

c. passing at least a portion of said hydrogen and carbon oxide-containing gas to said first reaction zone.

19. The process of claim 18, wherein said particulate 7 catalyst bed is a fluidized bed. 

2. The process of claim 1, wherein the weight of said alkali metal component (calculated as the metal) is between 1.0 and 35 weight percent of the total solids inventory of said bed.
 3. The process of claim 1, wherein the weight of said alkali metal component (calculated as the metal) is between 3 and 30 weight percent of the total solids inventory of said bed.
 4. The process of claim 1, wherein said alkali metal component (calculated as the metal) is between 4 and 25 weight percent of the total solids inventory of said bed.
 5. The process of claim 1, wherein said alkali metal component is an alkali metal compound which is at least partially reducible to the free metal.
 6. The process of claim 1, wherein said solid support is a non-gasifiable material.
 7. The process of claim 1, wherein said solid support is a refractory inorganic oxide.
 8. The process of claim 1, wherein said solid support is an inorganic oxide selected from the group consisting of silica, alumina, silica-alumina, magnesia, crude or partially purified bauxite or mixtures thereof.
 9. The process of claim 1, wherein said solid support is activated carbon.
 10. The process of claim 1, wherein said solid support is petroleum coke.
 11. The process of claim 1, wherein said catalyst comprises K2CO3 or Cs2CO3 deposited on or mixed with said support.
 12. The process of claim 1, wherein said first and second reaction zones are each maintained at a pressure between 200 and 800 psig.
 13. The process of claim 1, wherein said first reaction zone is maintained at an average temperature between 900* and 1,000*F. and said second reaction zone is maintained at an average temperature between 1,200* and 1,500*F.
 14. The process of claim 1, wherein an oxygen-containing gas is introduced into said second reaction zone.
 15. The process of claim 1, wherein a portion of the catalyst bed solids of the second reaction zone is passed to a separate heating zone and wherein at least a portion of the thus heated solids is recycled to said second reaction zone to provide a portion of the heat needed in that zone.
 16. The process of claim 1, wherein the hydrocarbon product is separated into lighter and heavier fractions and wherein at least a portion of the heavier fraction is recycled to said first reaction zone.
 17. The process of claim 1, wherein said hydrocarbon feedstream comprises at least 10 weight percent hydrocarbons having a boiling point above 900*F.
 18. A process for producing a partially desulfurized normally liquid hydrocarbon product and a hydrogen-containing gas from a hydrocarbon feed containing at least 10 weight percent hydrocarbons having a boiling point above 600*F. at atmospheric pressure, which comprises: a. contacting said hydrocarbon feed with a hydrogen and carbon oxide-containing gas in a first reaction zone containing a particulate catalyst bed comprising an alkali metal component, a non-gasifiable solid particulate support and an in-situ formed carbonaceous deposit on said support, wherein the alkali metal component (calculated as the metal) comprises at least 1.0 weight percent of the total solids inventory of said bed, said first reaction zone being maintained at a pressure above 150 psig and at an average temperature between about 700* and 1,100*F. to produce a normally liquid partially desulfurized hydrocarbon product, a hydrogen-containing gas and solid carbonaceous material, at least a portion of which deposits on said support during said contacting step; b. passing at least a portion of said particulate catalyst into a second reaction zone maintained at a pressure above 150 psig and at an average temperature between about 1,200*F. and 1, 500*F. and contacting the same with an oxygen-containing gas and with steam at a steam-to-hydrocarbon feed ratio of between 0.05 and 10 weight parts of steam to weight part of hydrocarbon feed of the first reaction zone to produce a hydrogen and carbon oxide-containing gas, and c. passing at least a portion of said hydrogen and carbon oxide-containing gas to said first reaction zone.
 19. The process of claim 18, wherein said particulate catalyst bed is a fluidized bed. 